JPS6176487A - N-substituted dicarboximide and herbicide containing same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (A is N or group shown by the formula II; X is halogen; Y is H, or halogen; U and V are O, or S; R is H, cyano, alkyl, alkenyl, etc.). EXAMPLE:3-[4-Chloro-2-fluoro-5-( isobutylthio )phenyl ]-1,5-tetrame-thylenehydantoin. USE:A herbicide. Showing improved herbicidal activity against weeds which are not easily controlled by well-known herbicides, having high safety to crops. PREPARATION:For example, a carbamoyl chloride derivative shown by the formula III is reacted with an aniline derivative shown by the formula IV in the presence of a base such as sodium carbonate, etc. at -20-150 deg.C to give an intermediate shown by the formula V, which is subjected to ring formation in the presence of an acid such as hydrogen chloride, etc. at -20-180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to specific N-substituted dicarboximides and herbicides containing them as active ingredients.

[Prior art]

Conventionally, it has been known that N-e substituted dicarboximides have excellent herbicidal activity.
76 contains 3-(It-rio-2-fluorophenyl)-/S-tetramethylenehydantoin,
The Japanese Patent Publication No. 7 KH14'-(4'-
chloro-2-fluorophenyl)-/, 2-tetramethyleneurazole is mentioned. However, slight modifications to these structures (type, number, position of substituents, etc.)
In many cases, the herbicidal activity or selectivity of a new compound is significantly different, and it is difficult to predict the herbicidal activity or selectivity of a new compound based on mere chemical structural similarity.

[Problem that the invention seeks to solve]

The present inventors have conducted extensive research to provide N-substituted dicarboximides that have superior herbicidal activity and crop safety compared to known N-substituted dicarboximides.
- A novel N-substituted dicarboxylic acid in which the substituted aryl is phenyl having a hydrogen atom or a norogen atom at the co-position, a norogen atom at the j-position, and having a specific substituent at the j-position [
[Means for Solving the Problem] The gist of the present invention is as follows: General formula (in the formula, A is a nitrogen atom or -OH-, X is a hydrogen atom), Y is a hydrogen atom or a nitrogen atom, and U and V each independently represent an oxygen atom or sulfur atom, R represents a hydrogen atom, a cyan group, an alkyl group, an alkenyl group, an alkynyl group, or an atom group, and n represents an integer from 2 to t. .

In the above substituents, R1 represents a hydrogen atom or a group to be alkylated.

In the above substituents, R2 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an aralkyl group, 13 is an alkyl group, and R4 and R5 are the same or different groups, a hydrogen atom, an alkyl group, an alkenyl group. R4 and R5 represent a saturated heterocyclic group which may contain one oxygen atom together with the nitrogen atom in the formula. ) N-substituted dicarboximides and herbicides containing these as active ingredients.

Next, the present invention will be specifically explained.

The N-substituted dicarboximide used as a herbicide in the present invention is represented by the general formula (1).

In the general formula (1), A is a nitrogen atom or -CH
- indicates. X represents a fluorine atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., preferably a chlorine atom or a bromine atom. Y is a hydrogen atom or a fluorine atom,
It represents a halogen atom such as a chlorine atom or a bromine atom, preferably a hydrogen atom or a fluorine atom. U and V each independently represent an oxygen atom or a sulfur atom;
When H-, V is preferably an oxygen atom.

R is a hydrogen atom; a cyano group; an alkyl group with a carbon number of -r, preferably an alkyl group with a carbon number of -g; an alkenyl group with a carbon number of -g, preferably an alkenyl group with a carbon number of 3 to 6; a carbon number of 3 to ≠alkynyl group, preferably propargyl group;
An alkoxyalkyl group having a total carbon number of λ to io, preferably an alkoxyalkyl group having a total carbon number of 3 to r, or a hydrogen atom, or an aralkyl group having a carbon number of /-ff, preferably a hydrogen atom or an alkylated group having a carbon number of /-ff. shows. In the formula, R2 is a hydrogen atom; an alkyl group with carbon number/-f, preferably an alkyl group with carbon number/-J; an alkenyl group with 2 to 2 carbon atoms, preferably an alkenyl group with 3 to ≠ carbon atoms; j is an alkynyl group, preferably a propargyl group; an alkoxyalkyl group with a total carbon number of - to IO, preferably an alkoxyalkyl group with a total carbon number of 3 to r, or an aralkyl group with a total of 7 to 7 carbon atoms, preferably a benzyl group;
-J is an alkyl group, preferably an alkyl group having co to j carbon atoms, R4 and R5 are the same or different from each other, and a hydrogen atom; an alkyl group having carbon numbers/~r, preferably carbon numbers/~
an alkyl group having a carbon number of t; an alkenyl group having preferably 3 to ≠ carbon atoms; an alkynyl group having 3 to j carbon atoms, preferably a propargyl group;
an aralkyl group having 7 to 3 carbon atoms, preferably a benzyl group whose α-position carbon may be substituted with 1 to 2 methyl groups, or an alkoxy group having 1 to 1 carbon atoms, preferably 1 carbon number;
-3 alkoxy group, or R4 and R5 represent a 5- to 7-membered saturated heterocyclic group which may contain one oxygen atom together with the nitrogen atom in the formula. n represents an integer of 2 to O, preferably an integer of 3 to j.

The compound of the present invention represented by general formula (1) can be produced using various raw materials, for example, according to the following reaction formula.

(II) (Ill) (IV) Y (In the above reaction formula, A, The above reaction is carried out by reacting the carbamoyl chloride derivative (II) with the aniline derivative (III) to form intermediate (IV), which is then cyclized. (1)
This is what you get. Intermediate (IV) was obtained by isolating it into 2
It may be used in the cyclization reaction at the beginning of the step, but in some cases it is also possible to lead to (I) without isolation.

The above first step reaction can be carried out without a solvent or with aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and chlorobenzene, chlorogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, diethyl ether, Ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, ketones such as acetone and ethyl methyl ketone, alcohols such as methanol, ethanol and propatool, N,N-dimethylformamide, N-methylpyrrolidone , in aprotic polar solvents such as dimethyl sulfoxide, sulfolane, acetonitrile, in solvents such as water, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate. , in the presence of a base such as triethylamine, pyridine, N,N-dimethylaniline, -
It is carried out at 20-/30°C.

The above second step reaction can be carried out without a solvent or in a solvent such as carboxylic acids such as formic acid and acetic acid in addition to the solvents listed as reaction solvents at the beginning of the step, or in a mixed solvent of hydrogen chloride, hydrogen bromide, In the presence or absence of an acid such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or a base such as potassium 1-butylade, sodium hydride, metallic sodium, etc. in addition to the bases listed as reaction catalysts in the above steps to the beginning, -, 20 to iroC.

The aniline derivative represented by general formula (m) can be synthesized, for example, according to the following formula.

1l- OY Y(III
C) (In the formula, R7 represents a lower alkyl group, R has the same meaning as above except for a hydrogen atom and a cyano group, and zl is a halogen atom such as a chlorine atom, bromine atom, or iodine atom, or methanesulfonate, p-) A sulfonate group such as luenesulfone. ) (V) (Vl) (■') Y (In the above reaction formula, AlX, Y, U%V, R and n have the same meanings as above, and R8 is a hydrogen atom, a lower alkyl group such as a methyl group, or an ethyl group. group or sodium ion,
Indicates cations such as potassium ions. ) The above reaction is performed using a cyclic amine (or hydrazine) derivative (
By reacting V) with a phenyl isocyanate (or inthiocyanate) derivative (■), an intermediate (■') is obtained, and by cyclization, II) is obtained. Intermediate (■') may be isolated and used in the τ first step cyclization reaction, but in some cases it is also possible to lead to (I) without isolation.

The above first step reaction may be carried out without a solvent or as described in (1) above.
-4'OS-7 in the solvent mentioned as the reaction solvent in the step
It is carried out at 60°C.

The first step cyclization reaction described above is carried out in the same manner as the cyclization reaction of reaction (1) above.

Phenyl isocyanate (
Intiocyanate) derivatives are the aniline derivatives (■
) can be obtained by reacting phosgene (thiophosgene) with phosgene.

Y (■) (M) (In the above reaction formula, U has the same meaning as above.) (■)
(Ia) (During the above reaction, X, Y, U, V%R
and n have the same meanings as above. ) The above reaction may be carried out without a solvent or in the solvent listed as the reaction solvent in step 1 of (1) above, in the presence or absence of a base such as the base listed as the reaction catalyst in step 7 of step (1) above. The reaction is carried out by reacting phosgene, trichloromethyl chlorocarbonate, thiophosgene, carbon disulfide, etc. at 1.20°C.

The raw material compound represented by the general formula (■) is the reaction formula (
It can be obtained by reacting the intermediate (■") synthesized according to 1) or (2) with a base.

(■“) (In the formula, R9 represents a lower alkyl group.) y (Ia) (In the above reaction formula, z2/'i is a halogen atom such as a hydrogen atom, a bromine atom, an iodine atom, or methanesulfone),
p-) Represents a sulfonate group such as luenesulfonate, and X, Y%U, V%R and n have the same meanings as above. ) The above reaction is carried out in the solvent listed as the reaction solvent in step (1) above, in addition to the base listed as the reaction catalyst in step (1) above, and a base such as hydrogen, sodium, etc. The reaction is carried out at -20 to /lO<0>C in the presence of.

The starting compound represented by the general formula (■) can be synthesized from the incyanate derivative (■) according to the following formula.

■ (Vl) +H2NNHOOR'0 (In the formula, RIG represents a lower alkyl group.)VY
VY (Ib) (Ic) (In the above reaction formula, A, In addition, in a solvent such as diglyme, in the presence or absence of an acid such as hydrochloric acid or acetic acid, or a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate, sodium borohydride,
Treating sodium cyanoborohydride, lithium aluminum hydride, and trihydride with a metal hydride compound such as lithium monobutoxyaluminum or a reducing agent such as a metal such as iron, zinc, or tin at -20~/jθ°C. It is done well.

VY (Ic) y (Id) (In the above reaction formula, A, X, Y, U, V, n and zl have the same meanings as above, and R has the same meanings as above except for hydrogen atoms and cyan groups.) The above reaction is carried out without solvent or in the first step of (1) above. Oh my god, it's 1 ゎ in the solvent. In addition to the base mentioned as the reaction catalyst for the seventh step,
Sodium hydride, potassium fluoride, cesium fluoride,
fC is carried out in the presence of a base such as metallic sodium, in the presence of an iodide such as sodium iodide or potassium iodide, or in the absence of fC at 1/θ to /40°C.

y (Is) Y (1f) (In the above reaction formula, A, X%Y, U, V, R'
Oyobi n has the same meaning as above, D' is -0R2, -8R
1 also has the same meaning as above, and R3, R4 and R5 have the same meaning as above. ) The above hydrolysis reaction is (:) water, water-methanol, water-
In a solvent such as ethanol, water-dioxane, in the presence of an acid such as hydrochloric acid or sulfuric acid, at θ to 120°C, or in a solvent such as formic acid or acetic acid, in the presence of an acid such as methanesulfonic acid or p-toluenesulfonic acid, at 10 to 120°C. /10°C.

1 (li) N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2. II, t-collidine, J
, 4-lutidine, pyridine or the like at 100-200° C. in the presence of lithium hydroxide, lithium bromide, lithium iodide, sodium iodide or the like.

The thus obtained compound of the present invention represented by the general formula (1) may exist in isomers such as optical isomers or diastereomers. In most cases, the isomers are obtained as a mixture containing all isomers, but can be obtained by various known methods (e.g., asymmetric synthesis, synthesis using starting materials with an asymmetric carbon source, optical resolution, recrystallization, Alternatively, each isomer can also be obtained by various chromatography methods such as column chromatography, thin layer chromatography, and high performance liquid chromatography).

Although the compound of the present invention can be used as a herbicide as it is, it is usually mixed with an inert liquid or solid carrier, and an appropriate surfactant is added thereto to form emulsions, powders, granules, tablets, etc. It is used in the form of irrigation agents, etc.

Liquid carriers include toluene, xylene, methylnaphthalene, cyclohexane, butanol, glycol, dimethyl sulfoxide, dimethylformamide, acetone,
Examples of tfC solid carriers include methyl imbutyl ketone, animal and vegetable oils, fatty acids, fatty acid esters, and water.
Examples include kaolin clay, talc, bentonite, diatomaceous earth, silica, calcium carbonate, and vegetable powders such as soybean flour and wheat flour. Furthermore, if necessary, it can be used in combination with other active ingredients, such as agricultural fungicides, insecticides, nematicides or other herbicides, plant growth regulators, soil conditioners and fertilizers. . In addition, to obtain a reliable weeding effect, adjuvants such as spreading agents, emulsifiers, wetting agents, and fixing agents may be appropriately mixed.

The amount of application of the herbicide of the present invention varies depending on the circumstances such as the S class of the compound used, the target weed, the treatment time, the treatment method, and the nature of the soil. /～! O grams, preferably θ, j-! A range of 10 grams is suitable.

[Effect]

The compounds of the present invention exhibit high herbicidal activity against many weeds in upland fields and paddy fields, while having almost no effect on crops. In other words, in the field, for example, whiteweed, pigweed, Japanese knotweed, hartade,
In rice fields, for example, azalea, common chickweed, Japanese snail, Japanese chickweed, Japanese grasshopper, Japanese millet, Japanese trifoliate, and other grasses are subjected to either pre-emergence treatment or growing season treatment. It can also be controlled by treatment. In addition, the compound of the present invention can be used in, for example, rice, dice, sunflower, cotton,
It can be used as a selective herbicide in the cultivation of crops such as potatoes, wheat, sugarcane, and corn.

Furthermore, the compound of the present invention can be used against weeds that have been difficult to control with existing herbicides, such as wild morning glory, Japanese yam, Japanese morning glory, wild mustard, Japanese grass, and Japanese grass in paddy fields. For example, firefly, water pyre, urikawa, etc.
It was found that it also has high herbicidal activity against black guinea pigs and the like. As described above, the compound of the present invention has the extremely excellent and surprising feature of having a very broad herbicidal spectrum and being highly safe for crops.

The scope of application of the compounds of the present invention is not limited to the above-mentioned types of plants, but can be used for other plants as well by the same application method.

〔Example〕

Next, the present invention will be explained in more detail by giving examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Actual M example/3-C'A・-chlorocofluoroS
Synthesis of -(inbutylthio)phenyl]- /,j-tetramethylenehydantoin -(isobutylthio)aniline/, 2Jrf, methyl N-(chlorocarbonyl)pipecolate/j-tetramethylenehydantoin and 10 ml of pyridine The mixture was stirred at room temperature for at hours. It was concentrated under reduced pressure, extracted with ethyl acetate, washed with dilute hydrochloric acid and then with water, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure,
The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane-2:j). fill
! ! Table L-/Compound (I6j) 0. I got Tade f. The NMR and IR of this compound were as follows.

' HNMR (cDat3) δ: /, 04 ((!, H
, d, J=jjH2), /, 2~Jj(7H, m), λ
, 7ri (JH, d, J=7 Hz), 2.1~
3. /(IH, m), 3. t~4(,/(IH,m),
J/ ~444 (IH, m), 7. ．． 2/(IH,d,
J=7H2), 71.2ri (IH, d, J=ri, rag
)IR(neat): , 2tO%/710. /73
01/IIIj.

/g30Cm-" Example ≠-[Hiro-chloro-1-fluoro-, f-(
/-(N,N-dimethylcarbamoy#)7'robylthio]phenyl]-/9. Synthesis of 2-tetramethyleneurazoleg-chloro-cofluoro-j-(/-(N,N-dimethylcarbamoyl)propyl Thiocoaniline 7, ra
t,/-(chlorocarbonyl)-2-(ethoxycarbonyl)-/, 2-tetramethylenehydrazine/no, 01
and 5 truts of pyridine was stirred at room temperature for 4' hours. It was concentrated under reduced pressure, extracted with ethyl acetate, washed with dilute sulfuric acid and then with water, and then dried over anhydrous magnesium sulfate.

The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:chloroform =, 2:J) to obtain /-[l-chloro-2-fluoro-6-(/ -(N,N-dimethylcarbamoyl)propylthio]phenylcarbamoyl)--2-(ethoxycarbonyl)-/, 2-tetramethylenehydrazine/0. Obtained OF.

Above /-[Hiro-10low λ-fluoro-j-(/-(
N,N-dimethylcarbamoyl)propylthio]phenylcarbamoyl]-2-(ethoxycarbonyl) -1
, 2-tetramethylenehydrazine 3.02 F, sodium methylate /, /lt and methanol I O
ml of the mixture was heated to reflux with stirring for 3.6 hours. The solvent was distilled off under reduced pressure, extracted with benzene, washed with dilute sulfuric acid and then with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate:hexane = 10:
The compound (A≠4) 2
．． /I got it. The NMR and IR of the compound were as follows.

'HNMR (0014) δ: 0. ri4j (JH
,t,d=7Hz),7.6～ko,,2(4H,m),
2. Za4 (4H, S), J, 4'~3.7 (pa, m)
, 3.7r ~3. ri4t(/a,m), 7.32
(IH, tl, J=ri, raz), 7.3 & (IH
, d, J=7.3Hz) Engineering R (neat): 2 110% /710. /730. /1,30, l≠ri0
．． /≠30cm-' Example J 3-(<<-chloro-2-fluoro-5-
Synthesis of (inpropylthio)phenyl] -/, j-tetramethylene-corchiohydantoin≠-chloro-no-fluoro! ! A mixture of -(bropylthio)phenylinthiocyanate 0.7 liters, pipecolic acid 0.3 liters and ethanol 10 Nl was heated to reflux with stirring for v hours. After distilling off the solvent under reduced pressure, the residue was It was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane=1:3) to obtain compounds (A3.z) θ, zatf listed in Table-7.

The NMR and IR of this compound were as follows.

'HNMR(0DO43)δ: /, Je(AH,a,
J=4. IH2), t, 3-2. r(AH,m), 2.
9~J, J (IH, m), 3, II/ ('H, 5ep
t, :J=A, jHz), 3.11IA (±H2
sept, , T=J, jHz), 3. Ri~4! , 2(
/Jm), 11.7~s, 0 (IH,m), 7.3
3 (IH, d, J = 2Hz), 7.31 ('-H, tl
, J==7H2), 7. '72 (8H, d, J=
7Hz) Engineering R (neat): 260. /7tθ, /4AIj
, /310cm Example ≠ 3-('amychloro-
Synthesis of 2-Truoroj(isopropylthio)phenyl] -/, 6-drimethylenehydantoin L-proline O1 ≠ 2, Sodium hydroxide o, s o
A mixture of water and water was cooled to 5° C., and a mixed solution of ≠-chloro 2-fluoro-(isopropylthio) phenyl isocyanate/sOf LU chlorobenzene 7d was added dropwise under W pressure. After the dropwise addition was completed, the mixture was stirred at room temperature for 7 hours. Ether was added to separate the aqueous layer, diluted hydrochloric acid was added to make it acidic, and the precipitate was extracted with ethyl acetate. The solvent was distilled off under reduced pressure, dioxane/d and 20 ml of 2N hydrochloric acid were added to the residue, and the mixture was heated under stirring and refluxed for 1 hour. After cooling, the mixture was extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane:/:, 2) to obtain 0.53t of the compound (16/) listed in Table-7. Ta. The NMR and IR of the compound were as follows.

'HNMR (cDct3) δ: /, 3.2 (tH, d
, J=t,,tH2),/,7~. 2. j (44H, m
), 3.2-4. Hiroshi (4 (H, m), 7.33 (/H
, d , J=riH2), 7,3J'(/H, d , J
=7 Hz) IR (KBrdiek): /73! %/4Jj1haL10cm-'Actual M example-t4'-(≠-chloro-fluoroj-(iapropylthio)phenyl-/2.Synthesis of 2-tetramethylene-3-thiourazole-chlorocofur Olow'(Iso7'.

virthio) phenyl thiocyanate 3.23f, /
A mixture of 2.371 ml of -(ethoxycarbonyl)-/, j-tetramethylenehydrazine and 20 ml of benzene was heated under pressure and refluxed for 5 hours. After concentrating under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane=i:s).
-[≠-chloro2-fluoro5-(isopropylthio]phenyl(thiocarbamoyl)]-111ethoxycarbonyl)-/,,2-tetramethylenehydrazine!
, 7 r f was obtained.

Above/-[l-chloro-2-fluoro-5-(isopropylthio)phenyl(thiocarbamoyl))-,2-(
A mixture of 11 ethoxycarbonyl-7,2-titramethylenehydrazine and 10 ml of cumene was heated under stirring and refluxed for 75 hours. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane =/:, 2) to give the compound () listed in the table. 0) 0. I got A jt.

The NMR and IR of the compound were as follows.

'HNMR(cDaz3)δ: /, J! (!H,d
,,r=4.5Hz),t,r~,z,z(4(H,
m),! ,4C2(/H,5ept,, J=,<,j
n, ), 3. t~3. ri(, za, m), 3. Ri~hiro, 2 (2H, m), 7. Jj (/H, d, J=ri, 5m5), 7.4tj (/H, d, J=7.jHz
) Engineering R (nujol mul): /763,1449
0%/1lsj.

/30! , /, 2rOQ7f(-' Example
Synthesis of isopropylthio)phenyl]-7,2-tetramethylene-3,j-dithiourazole l-(darkrolowcofluoros-(inpropylthio)phenyl(thiocarbamoyl))]-/,j-tetramethylene Hydrazine/Coco?, Potassium hydroxide O0
0.2 liters of carbon disulfide was added to a mixture of λlt 1 00 liters of water and ethanol/sml, and the mixture was heated and refluxed for t hours while stirring. It was concentrated under reduced pressure, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane=l:co) to form the compound (Aj 2 ) /, / shown in Table-7.
I got 7t. The NMR and rR of this compound were as follows.

'HNMR (cDat3) δ: /, 33 (AH, d,
J=t, jHz).

/, ri~, 2. J (44H, m), 3. u/ (/H
, 'eept, J=A, tH2), 3. Rihiro, J.
(j4H, m), 7.37 (/H.

d, J=riH2), 7.3ri(/H,d,,T=7H
'z) 工R(nujol m+rll): /'ta
so, /J/ocm-'Example 7 ≠-[μm
Synthesis of chlorocofluoro-S-(isopropylthio)phenyl] -/, -2-)rimethyleneurazole 4=-C≠-chlorocofluoro-j-(isopropylthio)phenyl]urazole/, -2, After stirring a mixture of potassium hydroxide o,tgr and 2oml of N,N-dimethylformamide at room temperature for 30 minutes, l,
7 tons of 3-dibromopropane was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate:hexane=2:/).
The compound listed in Table 7 (AjJ) 0.7
! I got t. The NMR and IR of the compound were as follows.

'HNMR(aDcz3)δ: /, 33(tH,d,
:f=t,lH2),x,po(koH,quint,
, f=7 Hz), 3,173 (lH.

5ept1J=J, jHg), jJJ(4(H, t, /
=7Hz), 7, JJ(lH, tl, J==ri, 5H2
), 7.1717 (lH, rl.

J=7. jHz) ru (KBr atsk): /7ro, /7kos
%iariO1/g/jcm-' Example t' J-(a-chloro-co, fluoro-j-mercaptophenyl)-/, s-tetramethylene-cochthiohydantoin synthesis 3-(<Z-chloro-2- 5.3 u f of S-tetramethylene-2-thiohydantoin (fluoro-j-4ocyanatophenyl)-/, S-tetramethylene-2-thiohydantoin were suspended in 7 synl of ethanol and treated with sodium borohydride o,rs at room temperature under stirring.
t was added little by little, and after the addition was complete, the mixture was further stirred for 75 minutes. The reaction mixture was poured into 300 ml of water, the precipitated crystals were collected and dried, and the compound (Aj O) 4 described in Table 7 was obtained.
A, IO2 was obtained. The NMR and IR of this compound are as follows.

'HNMR (cDcz3) δ: /, 2-2. j(A
H, m), -1ri, j, j(lH, m), 3.1r7
(lH,B), 3. Ri~hiro, Ko (lH, m),! ,7
3-j, Os (/H, m), 7.32 (lH, a,
J=riH2), 7.33 (8H, d, , T=7
H2), 7, J j (2H* d + J = 7
Ht;s) Engineering R (nujolmull): 2ar
θ, /7601 /4'ri511310cm-'' j-mercaftophenyl) -/,!-tetramethylene-cortiohydantoin o, t3t, allylpromide 0.36 f, potassium carbonate 0.4 A/f and acetone/jm/, heated under finger pressure for 3 hours, After cooling, the insoluble matter was separated in a furnace, the ν liquid was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: ethyl acetate:hexane=l:
3), and the compound (AJJ) listed in Table 0, j
I got Of. The NMR and IR of this compound were as follows.

'aNMR(aDet3)δ: /,? -, 2. t
(AH, m), 2. ri~j, J(lH,m), 311.
(KH, bd, I=7Hz), 3, Ri~! 10.2
(/H, m), p, q ~s, o(tH, m), s
, o S-s, 3(,2H,m),3. G~lr,l
(lH, m), 7, . 3/(lH,rl,J=riHz)
, 7.3o(-;H, d, J=7Hz), 7.3
3 and child H,')'=7Hi-IR(neat):
2ri 30% /7tj% /4! 0% 1310cm
-'Example 10 Synthesis of 3=[j-(/-carboxyethylthio)-≠-ri p-2-fluorophenyl)-/,S-tetramethylenehydantoin 3-[Hiro-chloro 3-(/-( ethoxycarbonyl)
A mixture of ethylthio]-2-fluorophenyl) -i, s-tetramethylenehydantoin/, jt, methanesulfonic acid O1≠2 and acetic acid 1 ornl was added under stirring to I1
The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate.

The solvent was distilled off under low pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethanol:chloroform=/:13), and the compounds listed in Table 7 (flat/chloroform) were purified.
2) 0. I got it.

The NMR and IR of the compound were as follows.

'HNMR(CDOt3)δ: /,63(3H,d,
:f=7Hz), 7.2~. 2.5 (AH, m), 2.
7-3. / (i H, m), JJA (lH, quar
t1J=7Hz), 3J-4,! (,zH,m), 7
．． ．． 341 (lH, rl,; J=riHz), 7. j7
(lH,d,,T=7H2),#,4(/(lH,be
)ER (KBr disk): 3010%/71rO
%/7201/≠ri0. /11.33cm Similarly, the compounds of the present invention listed in Table-/ were synthesized according to the method of the synthesis example shop listed in the table, and the physical properties were also obtained in Table-7.
It was shown to.

Next, examples of formulations of the compounds of the present invention will be shown. In addition, below is a copy.
"1%" means "1 part by weight" and "% by weight," respectively.

Formulation example/: Compound of the present invention JFy in Irrigation Table-1, 3 parts of Hiro θ, Carplex #♂θ (Shionogi Pharmaceutical Co., Ltd., trade name) 20 parts, N,
35 parts of N kaolin clay (Ueya Kaolin Co., Ltd., trade name),
Higher alcohol sulfate ester surfactant Tsurupol 1
5 parts of 07θ (Toho Chemical Co., Ltd., trade name) were blended and uniformly mixed and ground to obtain an irrigation agent containing active ingredient 11.

Formulation example, 2 parts granule Table 1 2 parts AI of the present invention, clay (Nippon Talc Co., Ltd. [) μm part, bentonite (:lv, 1riI Yoko Co., Ltd.) SS part, succinate surfactant Eyarol 0T
-1 (Toho Kagaku Co., Ltd., trade name) 2 parts were blended, mixed and pulverized, and then 70 parts of water was added and stirred. Knead this into a nest and use a granulator to make a diameter of 0. It was extruded through a hole in the A tran, dried at 60°C for 2 hours, and then cut into 1-2 lengths to obtain granules containing 2% of the active ingredient.

Formulation Example 3: 230 parts of Al, the compound of the present invention shown in the emulsion table -/, is dissolved in a mixed solvent consisting of 30 parts of xylene and 2j parts of dimethylformamide, and the polyoxyethylene surfactant Tsurupol 3006X (Toho Kagaku Co., Ltd., trade name) is added to this. 75 parts were added to obtain an emulsion containing 30% of the active ingredient.

Formulation example ≠: Floor pull agent Compound of the present invention in Table 7) 1 part ethylene glycol mixed in advance with 1130 parts of f5, 1 part of ethylene glycol, 1 part of ethylene glycol,
5 parts of a303.2 (Toho Kagaku Co., Ltd., trade name), 0.1 part of xanthan gum, and water were well mixed and dispersed.

Next, this slurry-like mixture was wet-ground using a sand grinder (Igarashi Kikai Co., Ltd.) to obtain a stable flowable agent containing 30% of the active ingredient.

〔effect〕

Test Example 1 Flooded soil treatment test: A 2,500/l are resin vat was filled with paddy alluvial clay loam, and after fertilization, an appropriate amount of water was added and plowed.

Seeds of Japanese millet, Kikashigusa, and Firefly were mixed into the Q and jCIn layers from the soil surface, and 1) s individuals of each of the tubers of Urikawa and Mizugaya cypress were transplanted per vat.

On the other hand, paddy rice seedlings at the Jj leaf stage (variety: Akinishiki, plant height: '
10. jc1n, Naega: Good) were shallowly planted with 93 plants per bat (7 plants) and 2 plants at an insertion depth of about 1 cm/cm. after that,
Approximately 3. The water depth of J CIn was maintained, and on the 3rd day after transplantation, granules containing the compound of the present invention as an active ingredient were obtained according to Formulation Example λ, and J-(a-Cl) were obtained in the same manner as Formulation Example λ. rhocofluorophenyl) -/, S-tetramethylenehydantoin (hereinafter abbreviated as comparative agent A), 4'-
(≠-chloro-2-fluorophenyl)-/,,2-?
) Ramethylene urazole (hereinafter abbreviated as comparative agent B).

) and S-(≠-chlorobenzyl)-N,N-diethyl-thiol carbamate (hereinafter abbreviated as Comparative Agent C) as active ingredients. A predetermined amount of granules were dropped onto a flooded surface. The plants were examined two days after the treatment, and the herbicidal effect and chemical damage were investigated on the second day after the chemical treatment.

The results are shown in Table-2. Furthermore, the evaluation of the herbicidal effect is was calculated and expressed as a herbicidal effect coefficient according to the following criteria.

In addition, the evaluation of drug damage is was calculated and expressed as a drug damage coefficient according to the following criteria.

Table-2 =55-160- */Sample agent A; Compound described in USP J.R. No. 76 *Co Comparative agent B; Test example of compound described in JP-A-33-4≠JtIr.7 λ Upland soil treatment test λ, A resin vat of 100 m/R was filled with upland black soil, and after fertilization, wheat, corn, and soybean were sown, and the soil was covered with 2 to 3 cm of soil.

In this soil layer, after homogeneously mixing Japanese grasshopper, Japanese blueberry, Japanese whiteweed, common Japanese knotweed, and Japanese knotweed, an irrigation agent containing the compound of the present invention obtained in Example 1 as an active ingredient and preparation example 1 was obtained. Wettable powders containing Comparative Agent A, Comparative Agent B, and 3-(J,!-dichlorophenyl)-/,/-dimethylurea (hereinafter abbreviated as Comparative Agent) as active ingredients were prepared by diluting them with water. ,/R Sawari Spraying Liquid-1
Spread an amount equivalent to #lOt evenly on the soil surface using a small power pressurized sprayer. Thereafter, the crops were cultivated in a greenhouse, and the herbicidal effect was investigated on the second day of bramble cultivation by spraying chemicals, and at the same time, chemical damage to each crop was also investigated.

The results are shown in Table-3. In addition, evaluation of herbicidal effect and phytotoxicity was carried out in the same manner as the criteria of Test Example/.

Table 3 Test Example 3 Stalk and Leaves Treatment Test A small polyethylene getter with an area of R and RSO was filled with black soil from the field, and after fertilization, crabgrass, Japanese blueberry, and Japanese knotweed were sown in separate pots.

Cultivation management was continued in the greenhouse, and when the growth level of the test plants reached the λ leaf stage for crabgrass and the 1st leaf stage for blueberry and Japanese knotweed, an emulsion containing the compound of the present invention obtained in Formulation Example 3 as an active ingredient was applied. Then, an emulsion containing 3, Kudichloropropionic acid anilide (hereinafter abbreviated as Comparative Agent E) as an active ingredient obtained in the same manner as in Formulation Example 3 was diluted with water, and the sprayed liquid amount was The equivalent I. was applied using a small powered pressurized sprayer. Thereafter, cultivation was managed in a greenhouse, and the herbicidal effect was investigated on the is day after the chemical spraying.

The droplets are shown in Table 1. In addition, the herbicidal effect was evaluated in the same manner as in Test Example 1.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent;
Patent Attorney Hase - 1 other person

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is a nitrogen atom or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X is a halogen atom, Y is a hydrogen atom or a halogen atom. , U and V each independently represent an oxygen atom or a sulfur atom, R is a hydrogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The base,
n represents an integer of 2 to 6. In the above substituents, R^1 represents a hydrogen atom or an alkyl group,
D represents -OR^2, -SR^3, or a group represented by ▼, which has a numerical formula, chemical formula, table, etc. Among the above substituents, R^2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an aralkyl group, R^3 represents an alkyl group, R^4 and R
^5 are the same or different from each other and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an alkoxy group, or R^4 and R^5 are a nitrogen atom and one oxygen atom in the formula. Indicates a saturated heterocyclic group which may contain. ) N-substituted dicarboximides represented by: (2) General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is a nitrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.), X is a halogen atom, and Y is a hydrogen atom or a halogen atom. , U and V each independently represent an oxygen atom or a sulfur atom, R is a hydrogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The base,
n represents an integer of 2 to 6. In the above substituents, R^1 represents a hydrogen atom or an alkyl group,
D represents -OR^2, -SR^3, or a group represented by ▼, which has a numerical formula, chemical formula, table, etc. Among the above substituents, R^2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an aralkyl group, R^3 represents an alkyl group, R^4 and R
^5 are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an alkoxy group, or R^4 and R^5 represent a nitrogen atom and one oxygen atom in the formula. Indicates a saturated heterocyclic group which may contain atoms. ) A herbicide containing an N-substituted dicarboximide represented by the following as an active ingredient.